Nanotube fabrication basis

ABSTRACT

A structure having a substrate, patterned metal layer and a catalyst island formed on the metal layer. The surface of the substrate upon which the metal layer is formed may be oxidized. As an illustrative example, the metal may be HfN and the catalyst island may be iron, nickel, or the like. The resulting structure may be placed in an environment having a carbon-containing gas, a temperature between 500 and 1200 degrees C., and an electric field. A nanotube may grow from the catalyst island. A method including the combining of hafnium and nitrogen may be used to make the nanotube growing structure.

BACKGROUND

The present invention relates to a deposition of material and particularly to high temperature deposition of metal on a wafer. More particularly it relates to such deposition for the fabrication of nanotubes.

Carbon nanotubes are a recent technological development. They may be hollow graphite tubules. In an isolated form, individual nanotubes may be useful for making microscopic electrical, mechanical and electromechanical devices. Single-walled nanotubes (SWNTs) are desirable. However, obtaining high quality, single-walled nanotubes has been generally a difficult task. Existing methods for the production of nanotubes often yield bundled forms of tangled and often multi-walled nanotubes. Such tangled nanotubes are very difficult to isolate into discrete elements for use in the fabrication of various electronic and/or devices.

SUMMARY

Development of a method, material and apparatus useful under high temperatures is needed for easy and reliable growth of carbon nanotubes (CNTs). The formation of nano islands is usually required to promote growth of SWNTs. Nano islands are typically formed by annealing a thin catalytic metal to a high temperature (i.e., 900 to 1000 degrees C.). Typically the formation of nanotubes by a high temperature anneal, leaves conductive islands but no macroscopic conductive path to permit external electrical contact to the nanotube. The use of another metal, typically forms an alloy with the catalytic metal preventing the formation of islands. Alternately, a metal can be applied to the nanotubes after growth but this process involves both pre- and post-CNT growth processing. The present invention solves these problems and meets those objectives. Metal islands having a particular material formed with an appropriate conducting metal have been developed to support the successful growth of nanotubes on a resulting structure for a reliable electrical connection to the nanotubes.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a wafer or substrate upon which the invention is made;

FIG. 2 shows an oxide layer on the substrate;

FIG. 3 reveals a layer of a conductive material on the oxide layer;

FIG. 4 shows the layer of the conductive material of FIG. 3 after its annealing in a gas;

FIGS. 5 a and 5 b show cross-sectional and plan views, respectively, of the patterned portions of the annealed conductive layer of FIG. 4;

FIGS. 6 a and 6 b show the passivation of the patterned portions of FIGS. 5 a and 5 b;

FIGS. 7 a and 7 b reveal sectional and top views of vias through the passivation layer to the patterned portions;

FIG. 8 shows patterned portions of a catalyst layer;

FIG. 9 reveals the annealing of the catalyst portions into islands; and

FIG. 10 shows external conductor connections and illustrates the growing of nanotubes.

DESCRIPTION

The development and application of a metal capable of withstanding deposition temperatures around 900 degrees Centigrade (C) that may be incorporated in metal islands for the growth of carbon nanotubes is one aspect of the present invention. To grow a carbon nanotube, it may be important to form metal islands to support the catalytic growth. The islands may be formed by exposing a thin metal such an iron (Fe) to high temperatures in an inert environment. At these high temperatures, the thin metal may ball up to form islands of a diameter on the order of the thickness. Small islands may yield single wall small diameter nanotubes. To make contact to these islands may require a patternable conducting metal. Most metals, such as aluminum (Al), that are used to form electrical connections, cannot withstand high temperatures. Many metals that can withstand high temperatures may anneal with other metals when exposed to high temperatures and thus prevent island formation.

A solution may be taking hafnium (Hf) metal, depositing it, and annealing it in nitrogen (N₂). The result may be HfN. This material may be conductive and support the formation of Fe and nickel (Ni) islands with a 900 degree C. inert anneal. Other catalyst metals may include, but are not limited to, molybdenum, cobalt, ruthenium, zinc and oxides of the metals. The catalyst materials may also include various alloys or mixtures of these metals including Fe and Ni, such as Mo—Fe. Carbon nanotubes may be formed on these structures. Briefly in sum, the Hf metal may be deposited and annealed in N₂ after patterning. Then a thin Fe or other catalytic metal may be deposited and patterned. This metal may be annealed in an inert environment to form islands on the HfN metal conductor lead material. The conductor material may be Hf_(x)N_(1-x) metal having a resistance between 10 ohms/sq and 10 Kohm/square. The present HfN is not a typical stoichiometric HfN. However, the HfN may be stoichiometric or non-stoichiometric. Other lead material may include, but are not limited to, Hf, transition metal nitrides, including ZrN, TaN, TiN, HfN, other conductive metals, Hf, conductive metals and oxides of the metals. The material may be ITO or some other conductive oxide.

For an illustrative embodiment, one may start with silicon (Si) wafer 11, as in FIG. 1. (The figures referred to in the present description are not necessarily made to scale.) Other wafer or other substrate materials that may be selected include, but are not limited to, silica, quartz, silicon nitride, sapphire and alumina. A thermal oxide (SiO₂) 12 may be grown on wafer 11, as indicated in FIG. 2. Substrate 11 may be substituted for layer 12. Oxide 12 may have a thickness of about or greater than 1000 angstroms. In lieu of the oxide, another insulative or semi-insulative material may be used as a layer 12. Next, in FIG. 3, a layer of Hf material 13 may be deposited on SiO₂ layer 12. The thickness of the layer of Hf material 13 may be between 500 and 1000 angstroms. Then the Hf material 13 may be annealed in an N₂ environment for about two hours at a temperature of 400 to 450 degrees C. However, the time duration may be longer or shorter and the temperature may be as low as 300 degrees C. or it may be greater than 450 degrees C. Also, another gas may be used for annealing. This should result in a layer 14 of HfN, as in FIG. 4. HfN layer 14 may be patterned as conductor strips 15 for external connections. Cross-sectional and plan views are shown in FIGS. 5 a and 5 b, respectively. The resultant exposed materials, that is, a portion of layer 12 and HfN conductor strips 15 on the wafer, may be passivated with a layer 16, for example, silicon nitride or the like, such as other passivation materials. Passivation layer 16 is shown in the cross-sectional and plan views of FIGS. 6 a and 6 b. Then vias 17 may be etched or cut through passivation layer 16 to HfN strips 15, for external conductor 25 connections. Also, vias 18 may be etched or cut through passivation layer 16 to HfN conducting strips 15 for connection to catalyst islands 21 of FIG. 9. Vias 17 and 18, shown in FIGS. 7 a and 7 b, may be made with for example a plasma etch.

A thin catalyst layer 19, such as Ni or Fe may be deposited on and in vias 18 to an exposed portion of HfN strip 15 at room temperature, such as with sputtering. Other appropriate materials may instead be deposited. That layer 19 of catalyst material may be between 50 and 100 angstroms thick. Then, the catalyst may be patterned with liftoff or by milling to result in catalyst portions 19, as indicated in FIG. 8. Afterwards, the patterned catalyst deposited layer 19 may be annealed in a forming gas composed of about 15 percent of hydrogen and 85 percent of nitrogen, for about 30 minutes at about 900 degrees C. However, various gases and mixtures at a temperature with a range between 500 and 1200 degrees for a period ranging between 15 minutes and two hours may suffice for annealing. This annealing may form an island 21 of each catalyst material portion 19, as illustrated in FIG. 9. Also, during the annealing, structure 20 may be purged of gases such as oxygen.

After the annealing, the gas may be switched to methane (at a rate of 1700 or 850 sccm) and H₂ (at a rate of 1700 or 850 sccm) for a growing of a carbon nanotube. Other carbon-containing gases may be used in lieu of methane. (The abbreviation “sccm” means standard cubic centimeters per minute. “Standard” means that the measurement is referenced to zero degrees C. at 760 Torr, i.e., 1 atm pressure.) Methane may be also mixed in with the forming gas at a ratio of one to one at about 1000 sccm. The flow rates may be other than stated here for satisfactory annealing and growing nanotubes. An electric field of about one volt per micron of gap 22 (in FIG. 9) may be applied during the growing of the nanotubes. For instance, a bridging of a 10 micron gap with a growing nanotube would use a 10 volt electric field. Other electric field intensities may be incorporated. As a result, a nanotube 23 may be grown connecting two islands 21, as illustrated in FIG. 10. Or an unconnected nanotube 24 may be grown for one purpose or another. Conductors 25 may be bonded, soldered, or attached in some fashion to HFN conducting strips 15, respectively.

Although the invention has been described with respect to at least one illustrative embodiment, many variations and modifications will become apparent to those skilled in the art upon reading the present specification. It is therefore the intention that the appended claims be interpreted as broadly as possible in view of the prior art to include all such variations and modifications. 

1. A method of making a structure for growing nanotubes, comprising: growing a thermal oxide on a surface of a silicon wafer, depositing a layer of Hf on the thermal oxide; annealing the layer of Hf in N₂ to obtain a layer HfN; patterning the layer of HfN; forming passivation layer on the layer of HfN; cutting vias through the passivation layer to the layer of HfN; depositing a catalyst material in the vias; patterning the catalyst metal; and annealing the catalyst metal to form catalyst islands.
 2. The method of claim 1, wherein: the layer of Hf is annealed in N₂ for more than one hour at a temperature greater than 300 degrees C.; and the catalyst material is annealed in a forming gas.
 3. The method of claim 2, wherein the catalyst material is annealed at a temperature greater than 700 degrees C. for a period of time greater than fifteen minutes.
 4. The method of claim 3, wherein the forming gas comprises H₂ and N₂.
 5. The method of claim 4, wherein the catalyst material is selected from a group consisting of iron, molybdenum, cobalt, nickel, ruthenium, zinc and oxides thereof.
 6. The method of claim 5, further comprising: placing an electric field in a vicinity of the catalyst islands; maintaining the temperature greater than 500 degrees; and maintaining the forming gas in the vicinity of the catalyst islands to grow a nanotube.
 7. The method of claim 5, further comprising: placing the catalyst islands in an electric field; maintaining the temperature greater than 500 degrees; and placing the catalyst islands in an environment comprising carbon-containing gas.
 8. The method of claim 7, wherein the carbon-containing gas is methane.
 9. The method of claim 8, further comprising maintaining the environment of claim 7, until a desired nanotube is grown.
 10. A structure comprising: a substrate; an oxide layer on the substrate; an HfN layer on the oxide layer; a passivation layer on the HfN layer, having at least one via through the passivation layer to the HfN; and a catalyst island formed on the at least one via connected to the HfN layer.
 11. The structure of claim 10, wherein the catalyst island is placed in an environment having a carbon-containing gas, a temperature greater than 500 degrees C. and an electric field.
 12. The structure of claim 11, wherein the environment is maintained until a desired nanotube is grown.
 13. A structure comprising: a substrate; an insulating layer on the substrate; an HfN layer on the insulating layer; a protective layer on the HfN layer; and at least one catalyst island in contact with the HfN layer.
 14. The structure of claim 13, wherein the catalyst comprises at least one metal selected from a group consisting of iron, nickel, cobalt, zinc, molybdenum, ruthenium and oxides thereof.
 15. The structure of claim 14, wherein placing the structure in an environment comprising: a carbon-containing gas; an electric field; and a temperature greater than 500 degrees C.
 16. The structure of claim 15, maintaining the environment until a nanotube is grown.
 17. Means for making a structure for growing a nanotube, comprising: means for providing a substrate; means for at least partially insulating a surface of the substrate; means for forming a layer of HfN on the surface of the substrate; means for passivating a surface of the layer of HfN; and means for forming at least one catalyst island having contact with the layer of HfN.
 18. The means of claim 17, wherein that at least one catalyst island comprises a material selected from a group consisting of iron, nickel, zinc, molybdenum, cobalt, ruthenium and oxides thereof.
 19. The means of claim 18, wherein the substrate comprises a material selected from a group consisting of silicon, silica, alumina, quartz, sapphire, and silicon nitride.
 20. The means of claim 19, further comprising: means for subjecting the at least one catalyst island to a temperature greater than 500 degrees C.; means for subjecting the at least one catalyst island to a carbon-containing gas; and means for subjecting the at least one catalyst island to an electric field.
 21. The means of claim 20, further comprising means for sustaining the temperature, the carbon-containing gas and the electric field until a nanotube is grown.
 22. A method for making a structure comprising: forming HfN material on a substrate; and forming at least one catalyst island on the HfN material.
 23. The method of claim 22, further comprising: placing the structure in a carbon-containing gas; and placing the structure in an environment having a temperature greater than 500 degrees C.
 24. The method of claim 23, placing the structure in an electrical field.
 25. The method of claim 24, further comprising growing a nanotube.
 26. An apparatus comprising: an insulating substrate; a first material deposited on the substrate; and an island of a second material formed on the first material.
 27. The apparatus of claim 26, wherein the first material is selected from a group of transition metal nitrides, ZrN, TaN, TiN, HfN, conductive nitrides, Hf, conductive metals and oxides thereof.
 28. The apparatus of claim 27, wherein the first material is stoichiometric.
 29. The apparatus of claim 27, wherein the first material is non-stoichiometric.
 30. The apparatus of claim 27, wherein the second material is selected from a group of Fe, nickel, molybdenum, cobalt, ruthenium, zinc, and oxides, alloys and mixtures thereof.
 31. The apparatus of claim 27, wherein the first material is ITO.
 32. The apparatus of claim 27, wherein the first material is a conductive oxide.
 33. The apparatus of claim 30, wherein the substrate comprises a material selected from a group of silicon, silica, quartz, silicon nitride, sapphire, and alumina.
 34. The apparatus of claim 33, further comprising a nanotube extending from the island. 